Silicones containing an amido group and method of preparing same



United States Patent 3,440,261 SILICONES CONTAINING AN AMIDO GROUP AND METHOD OF PREPARING SAME John C. Saam, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Filed Mar. 18, 1965, Ser. No. 440,921 Int. Cl. C07f 7/02, 7/04; C08g 31/02 US. Cl. 260448.2 24 Claims ABSTRACT OF THE DISCLOSURE Silanes and siloxanes containing an amido group in the side chain are disclosed as new compounds. In addition, the method of preparing these amido functional silicones by the alkaline hydrolysis of imidazoline functional silanes is also claimed. The compounds and copolymers are useful for treating glass cloth to improve the strength of laminates made therefrom, as textile treating agents to improve the dyeability of the textile, and as creaseproofing and water repellent agents for textiles.

This invention relates to silicones containing an amido group as a part of a substituent group on the silicon atom and to a method of preparing such silicones.

More specifically, this invention relates to compounds of the formula wherein R is a divalent hydrocarbon radical free of aliphatic unsaturation,

Y is selected from the group consisting of the hydrogen atom and monovalent hydrocarbon radicals free of aliphatic unsaturation,

R" is a monovalent hydrocarbon radical, and

a has a value from 0 to 3,

and their preparation by the hydrolysis, under alkaline conditions, of a silane of the formula wherein R, Y, R" and a are as defined above and R is an alkyl radical containing from 1 to 4 carbon atoms.

This invention further relates to copolymers containing siloxane units of the formula u H q wherein R, Y and R are as defined above and b has a value from 0-2, and siloxane units of the formula wherein R" is selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, and c has a value from 0 to 3. The invention also relates to the preparation of such copolymers by the cohydrolysis and cocondensation, under alkaline conditions, of silanes of the formula wherein R, Y, R", R and b are as defined above, and a compound (B) selected from the group consisting of silanes of the formula R Si(0R') and siloxanes con- 3,440,261 Patented Apr. 22, 1969 with the radicals containing 3 or 4 carbon atoms being the most preferred.

The Y group in the above formula can either be a hydrogen atom or a monovalent hydrocarbon radical free of aliphatic unsaturation. Thus Y can be an alkyl radical such as a methyl, ethyl, propyl, butyl, amyl, octyl, decyl, dodecyl, octadecyl or a myricyl radical; a cycloalkyl radical such as a cyclopentyl or a cyclohexyl radical; an aryl radical such as a phenyl, xenyl or a naphthyl radical; an aralkyl radical such as a benzyl, 2-phenylethyl or a Z-phenylpropyl radical, or an alkaryl radical such as a tolyl, xylyl or a mesityl radical. It is generally preferred that the Y groups contain from 1 to 6 carbon atoms when they are a hydrocarbon radical, and most preferably the Y groups on the carbon atoms that bridge the two nitrogen atoms are hydrogen atoms.

R" in the above formula can be any monovalent hydrocarbon radical. Suitable examples of such hydrocarbon radicals are set forth in the description of Y above. In addition to the above radicals, R" can be, for example, an alkenyl radical such as a vinyl, allyl, hexenyl or an octadecenyl radical; an alkynyl radical such as a propynyl or an ethynyl radical; or a cycloalkenyl radical such as a cyclopentenyl or a cyclohexenyl radical.

In the silanes, R is an alkyl radical containing from 1 to 4 carbon atoms. Thus R can be a methyl, ethyl, propyl, isopropyl or a bntyl radical.

The R radical can be any monovalent hydrocarbon radical or substituted monovalent hydrocarbon radical. By Way of example, R can be an alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, aralkyl or an alkaryl radical or the corresponding halogenated, cyano-substituted or aminated radical. Specific examples of some of these groups are given under the definitions of Y and R" above. Specific examples of suitable groups not described under Y and R" are the cyanoethyl, delta-cyanobutyl, omegacyanooctadecyl, gamma-aminopropyl, delta-aminobutyl, omega-aminododecyl, H NCH CH NHCH CH CH H NCH CH NHCH CH (CH CH aminophenyl, 3- chloropropyl, 4-bromobutyl, 3,3,3-trifiuoropropyl, perfluorovinyl, chlorocyclohexyl, dichlorophenyl and the bromobenzyl radicals.

3 The siloxanes that can be used in preparing the copolymers of this invention are well known in the art. Generally speaking, the hydrolyzable groups are present as part of the endblocking groups but this is not an essential requirement. Even when this is the case, some such hydrolyzable groups will usually be found along the polymer chain. Examples of such hydrolyzable groups are the alkoxy groups (methoxy, ethoxy and isopropoxy), the acyloxy groups (acetoxy and propionoxy) and the cellosolvoxy groups (CH CH OCH and -CH CH OCH CH The term hydrolyzable group as used herein is also intended to include the hydroxyl group even though it is not hydrolyzable in the strictest definition of the term.

The compounds and copolymers of this invention are useful, for example, for treating glass cloth to improve the strength of laminates made therefrom. They are also useful as textile treating agents to improve the dyeability of the textile, particularly with acid dyes. These compounds and copolymers can also be reacted with amines such as melamine, triazine or substituted triazine to obtain creaseproofing and Water repellent agents for textiles. Other uses of the products of this invention will be apparent to those skilled in the art.

The compounds of this invention are prepared by the hydrolysis of silanes of the Formula 2, given above, under alkaline conditions. Such silanes have been fully described, along with their method of preparation, in copending application Ser. No. 249,314, now US. Patent 3,373,137 of John C. Saam, filed Jan. 4, 1963 and entitled Nitrogen- Containing Organosilicon Compounds and Their Preparation. The disclosure of this copending application is incorporated herein by reference.

By alkaline condition, it is meant herein that the aqueous solution of the silane being hydrolyzed must have a pH greater than 7. However, it is generally preferred that a pH of at least 9 be employed in order to obtain a reasonable reaction rate. In some instances the silane being hydrolyzed will be basic enough to render the solution alkaline whereas in other instances it Will be necessary to add enough of an alkaline material such as, sodium hydroxide, potassium hydroxide, calcium oxide, soium bicarbonate, potassium carbonate, guanidine, dimethylamine, methylamine, pyridine or ammonia, to make the solution alkaline. Of course, in some instances it will be desirable, as should be obvious to those skilled in the art, to add such an alkaline substance to the solution even if the silane per se is basic.

In order that those skilled in the art may better understand how the instant process can be carried out and how the new products can be made, the following examples are given by way of illustration and not by way of limitation.

'Example 1 A mixture of 10 g. of

was obtained. This compound was found to have a neutral equivalent of 211.8 (theoretical 211).

Example 2 55.6 g. of

was mixed with 14.0 ml. of water. The reaction was exothermic. The excess was water removed in a vacuum of about 20 mm. of mercury at room temperature. The remaining water was then removed at 1.0 mm. of mercury pressure at room temperature over a period of 45 hours.

The product,

had the following properties.

Found Theoretical Refractive index no Density (1 Specific refraction R Neutral equivalent. Percent Si 13 Example 3 Solutions of in isopropanol were prepared. These solutions were then added to water buffered on the alkaline side with disodium phosphate, the resulting mixtures vigorously shaken, and then allowed to stand at room temperature. The re sulting products were Example 4 When the silanes below are substituted in the process of Examples 1 or 2, the indicated products are obtained.

Silane Product Example 5 A copolymer containing about 85 mol percent of 25 (CH SiO units and about 15 mol percent of II II O (CHa)zSiCH2CH(CH3) CHzNHCHaCHzN-CH I? OmSiONHOHzCIhN-C-H units can be prepared when a hydroxyl endblocked polydimethylsiloxane and the silane I l (CHaO)(CHa)zSiCH2CH(OH )CH2NCHzOHzN=CH are mixed under alkaline conditions.

Example 6 I (CH3) CzH5Si(O CHa)z II CHz= CH(CH )S(O CH III OFaCH2CHz(CH )Si(O C211 Siloxane Units (CH3) C2H5SiO CF3CHzCH2(CH3)SiO Cn n m IV Co s( a) a 7)2 CaHs( 3) (CHmSiO CH3 3)3 1/2 O H CzHg H5=NCH CH(CHa)N(CH2)-1Si(C2H5) (O CHIQZ Bi -1 1CH2CH(CH3)NH(CH2)4SiO V (CH3)3SiO CH3 (CHLQaSiCh/g Si(O CzH5)4 SiOz Silanes Siloxane Units VIII CeH3Cl Si(O (EH93 CsHaClzSiOa/n (CaH5)2Si(OH)2 92 (CH Si(O CH (01192310 IX H2N(CH )aSi(0 021193 HZNwHmsiOa/Q NCCH CHACHQSKO CzH5)2 NCOHzCHz(CH;)SiO

t? 1 Hmwmnsnom) (0 0mm HC-NCHzCH2N(CH2)4SlO Example 7 That which is claimed is: one gram of 1. A process for making compounds of the formula R. H O (CH O) Si(CHz)3NCH CH2N=GH l g T was diluted to 20 g. with 0.1% acetic acid whereupon a wherein clear solution of R is a divalent hydrocarbon radical,

l H Y is selected from the group consisting of the hydrogen Si(CH NHOH CH N cH atom and monovalent hydrocarbon radicals free of 5 aliphatic unsaturation containing from 1 to 6 carbon toms 1 t d to ,f. 2 3 g zv i th i) l gi ai ii gid then further dlu e R is a monovalent hydrocarbon radical containing Heat cleaned 181-style glass cloth was dipped into if g s gg ig fig g carbon atgms and no the above solution, air dried for 45 minutes and then ahasavalue from?) t 5 car ona omsan heated for 7 minutes at 110 C. The glass cloth (237.5 g.) O was then dipped into a mixture of 213 5 v of an acetone process compnsmg hydrolyzmg under alkaline solution of DER 331 containing 60% resin solids or dltlonsasllane of the formula 128.1 g. resin and 18.55 g. of meta-phenylenediarnine (2) R", (14.5 parts per hundred parts ICSIH): DER 331 1s a low E; molecular weight liquid epoxy resin produced by the reaction of epichlorohydrin and bisphenol A. DER 331 l f R, R and a f a5 defined above, and has an epoxide equivalent weight of 187-193, a viscosity R 15 an alkyl Tadlcal Contalnlng from 1 t0 4 carbon of 11,000-16,000 cps. and a specific gravity of 1.17. atoms- After dipping, the cloth was air dried about 15 minutes 40 The Process of clam! 1 Wherfilfl 1S and then precured for another 15 minutes at 110 C. The 0 cloth was then cut into 8" squares and 14 of these g squares stacked into a laminate by laying up the warp OZIZSPIPNHCHZCEN" threads at 90 angles in alternate layers. This assembly and 15 was then press cured for 30 minutes at 150 C. under 30 pounds per square inch of pressure and then hot released. )3 2CHzN=CY The resulting laminate was tested for flexural stren th 3 The recess of claim 2 I wh employmg US. Federal Specification L-P 406b, Method andYis a gg g i R is 1031 and for compress ve strength employ1ng Method The process of claim 1 wherein (1) is 1021 of the same speclfication. These properties were also measured on samples of the laminates after they had been boiled in water tor two hours, then cooled to OSi-CHzCEKCHa)CHzNHCHzCIIzI IgH room temperature and wiped dry. The results of the d 2 latter test are referred to as Two hour boil in the an 15 table below. This test is recognized as being roughly the H: equivalent of standing in water at room temperature for 0 (CH O) SFCH CH CH on m one month. The two hour boil results times 100, and 3 z 2 a) r. CHZN CH then divided by the as molded (dry) results is the percent 5- The process of claim 1 wherein (1) is retention of the strength. (CH) For purposes of comparison, the above procedure was i 3 H repeated with the exception that the glass cloth Was not ()0 0mSi-CH1OH(CH:)CHz-NHCHzCHzNCH pretreated in any way prior to its being dipped in the epoxy resin. (2) 15 Each of the flexural strength results reported below are (03:01 an average obtained from four laminates tested and each CH OSi--CH CH(CH3)CHzNCH CH N=CII of the compressive strength results are an average obmi d from h 1 i 6. The process of claim 1 wherein 1) is I Flexural Strength Compressive Strength and (2) is RUSi R NHCHCHZN(i Y Glass Two Percent Two Percent Dry lgtzhilr Retention Dry flgglilll Retention RII: i R fiC HZ(E E Y iriiriiiIIjI 9153 2:338 333% 311533 53:231. 32:? The Pmcess claim wherein is GHQ-w R 7 1s CH CH CH and Y is a hydrogen atom.

9 8. A compound having the formula RI!l I H OmSiCHzCHzCHzNHCHzOHgN-CH 11. A siloxane of the unit formula 12. A siloxane of the unit formula 13. The silane O I (CHa)3SiCHzCHzCHzNHCHzCHzN-AH 14. A process for making copolymers containing siloxane units of the formula wherein R is a divalent hydrocarbon radical,

Y is selected from the group consisting of the hydrogen atom and monovalent hydrocarbon radicals free of aliphatic unsaturation containing from 1 to 6 carbon atoms,

R" is a monovalent hydrocarbon radical containing no more than 30 aliphatic carbon atoms and no more than 12 aromatic carbon atoms, and

b has a value from 0-2, and siloxane units of the formula wherein R is selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, there being no more than 30 aliphatic carbon atoms and no more than 12 aromatic carbon atoms in R, and

c has a value from '0 to 3, said process comprising cohydrolyzing and cocondensing under alkaline conditions, silanes of the formula 10 wherein R, Y, R" and b are as defined above and R is an alkyl radical containing from 1 to 4 carbon atoms, and a compound (B') selected from the group consisting of silanes of the formula R" Si(OR) wherein R, R' and c are as defined above, and siloxanes containing non-acidic hydrolyzable groups and R radicals attached to the silicon atoms.

15. The process of claim 14 wherein (A) is and in (B) and (B') R is selected from the group consisting of the methyl, phenyl and 3,3,3-trifluoropropyl radicals.

16. The process of claim 15 wherein R is Y is a hydrogen atom and c is about 2.

17. The process of claim 15 wherein R is Y is a hydrogen atom and c is about 2.

18. A copolymer containing siloxane units of the formula R"b H O R is a divalent hydrocarbon radical,

Y is selected from the group consisting of the hydrogen atom and monovalent hydrocarbon radicals free of aliphatic unsaturation containing from 1 to 6 carbon atoms,

R" is a monovalent hydrocarbon radical containing no more than 30 aliphatic carbon atoms and no more than 12 aromatic carbon atoms, and

b has a value from 0-2, and siloxane units of the formula wherein R is selected from the group consisting of monovalent hydrocarbon radicals and substituted monovalent hydrocarbon radicals, there being no more than 30 aliphatic carbon atoms and no more than 12 aromatic carbon atoms in R', and c has a value from 0 to 3. 19. The copolymer of claim 18 wherein (A) is and in (B), R" is selected from the group consisting of the methyl, phenyl and 3,3,3-trifiuoropropyl radicals.

20. The copolymer of claim 19 wherein (A) is and in (B), c is about 2.

21. The copolymer of claim 19 wherein (A) is and in (B), c is about 2.

11 12 22. The copolymer of claim 18 wherein (A) is References Cited E UNITED STATES PATENTS OSi-R-NHCHzCHzN-CY 2,919,173 12/1959 Roff 88 XR and in (B), R' is selected from the group consisting 2,971,364 2/ 1961 Speier 11 -124 XR of the methyl, phenyl and 3,3,3-trifluoropropyl radicals. 5 2,929,329 3/ 1960 M rfih use 260-4482 23. The copolymer of claim 22 wherein (A) is ,088,8 7 5/1963 Pines 117-75 XR OH H 0 3,174,987 3/1965 Simmler et al. 26O448.2

n 0SiCH2CH2CH2NHCH2CH2NCH 1 TOBIAS E. LEVOW, Primary Examiner. and in (B),CiS about 2. 0 J P POD ORSKI A t t E 24. The copolymer of claim 22 wherein (A) is G ms xammer' 1H1 H 0 US. Cl. X.R. OSiOHfiHWHQCHZNHCHZCEBN-OH 260--448.8, 46.5; 117 124, 139.4; 106-13 and in (B), c is about 2. 

